CN103943725B - A kind of metallic oxide nanocrystal palpus/Si matrix material and catalytic growth method thereof - Google Patents
A kind of metallic oxide nanocrystal palpus/Si matrix material and catalytic growth method thereof Download PDFInfo
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- 239000011159 matrix material Substances 0.000 title claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 2
- 229920005591 polysilicon Polymers 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000009466 transformation Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002096 quantum dot Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract 1
- 231100000289 photo-effect Toxicity 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000004246 zinc acetate Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of metallic oxide nanocrystal palpus/Si matrix material and catalytic growth method thereof. This invention tool has the following advantages: 1. nano whisker/Si matrix material shape the looks of growth are evenly controlled, and optical stability is good and has better resistance to elevated temperatures. 2. can significantly promote various performance parameters and the photoelectric transformation efficiency of silica-based solar cell sheet. 3. technique is simple, strong operability, cheaper starting materials and reusing, and production cost is low, high efficiency, is applicable to that industry is big produces. Technique of the present invention mainly uses catalytic chemistry deposition method, formed one layer of shape looks evenly controlled, thickness be about the metallic oxide nanocrystal palpus/Si matrix material of 20-100nm. Utilize the sunken photoeffect of nanometer crystalline substance/quantum dot, confinement effect and multiple exciton effect etc., significantly improve the photoelectric transformation efficiency of crystal-silicon battery slice.
Description
Technical field
The present invention relates to silicon based composite material, nanotechnology, area of solar cell, specifically a kind of metallic oxide nanocrystal palpus/Si matrix material and catalytic growth method thereof.
Technical background
In the solar cell of numerous type, the brilliant solar cell of silicon occupies current light volt market more than 90%, is the photovoltaic device that technology is the most ripe. The theoretical conversion efficiency value of crystal silicon solar batteries can reach 31%, and the highest transformation efficiency of Experimental report is 24.7%, and the finished product battery efficiency of suitability for industrialized production is lower, monocrystalline about 17%, polycrystalline about 15%. Improve further the brilliant conversion efficiency of solar cell of silicon and reduce production cost be current solar cell Application and Development the most important be also the most effective direction.
Crystalline silicon is a kind of indirect gap semiconductor material, and energy gap 1.12eV, can only effectively absorb the solar photon of 600��1000nm, higher than the solar photon of energy gap with the form loss of " thermoelectron ". This just greatly reduces the photoelectric transformation efficiency of crystal silicon solar batteries. In addition, the luminous reflectance effect of cell panel also reduces the efficiency of light absorption of crystal silicon battery. For improving the efficiency of conversion of solar cell, surface-texturing, surface etching, launch site passivation, subregion doping, sputtering Si need to be carried out3N4The steps such as antireflective coating, this just considerably increases production cost; And, after said process, the photoelectric transformation efficiency of crystal silicon solar batteries does not obtain basic improvement, thus limits the fast development of light volt industry.
Nanometer crystalline substance or quantum dot have absorption spectrum width, uptake factor height, the absorption spectrum that can widen crystal silicon battery; In addition, nanometer crystalline substance or quantum dot have and slow down hot carrier cooling and electronics is speeded the effect in Henan, it is possible to make hot carrier before being cooled to band edge, they are caught utilization. Nanometer crystalline substance or another function of quantum dot are quantum confined effect: can produce multiple exciton so that quantum yield can more than 100%. So, nanometer crystalline substance or quantum dot being applied to is the most effective approach improving existing photovoltaic cell photoelectric transformation efficiency on crystal silicon solar batteries.
Summary of the invention
It is an object of the invention to by catalytic chemistry deposition method, on crystal silicon solar batteries sheet, fast-growth a layer thickness is about the metal oxide semiconductor nano whisker of 20-100nm, significantly improves spectral absorption efficiency and the photoelectric transformation efficiency of cell piece.
The technical scheme of the present invention is:
A kind of metallic oxide nanocrystal palpus/Si matrix material catalytic growth method, concrete steps are as follows:
A) configuration of solution: the catalyst solution of (1) 0.0001mol/L��1mol/L, adds the hydrofluoric acid of 1mol/L��6mol/L; (2) hydrofluoric acid of 0.05mol/L��6mol/L/hydrogen peroxide etching solution; (3) the nanowhisker growth mother liquor of 0.0001mol/L��5mol/L metal ion;
B) pre-treatment of cell piece: be impregnated in catalyst solution by the crystal-silicon battery slice making p-n junction 1��200s, makes cell piece surface form metal oxide crystal seed; Being immersed to 1��200s in etching solution after taking-up, carry out anisotropic etch, draining after taking out, blows dry;
C) growth of nano whisker: be moved rapidly in mother liquor by above-mentioned cell piece 1��100s, carries out the growth etching of nano whisker;
D) carrying out washing treatment: with washed with de-ionized water 1��5min, blow dry;
E) thermal treatment: by the cell piece after washing at 100 DEG C��400 DEG C thermal treatment 1��30min.
Described catalyst solution is the one in copper, silver, platinum or the gold muriate of metal, acetate or nitrate.
Described cell piece pre-treatment need to carry out anisotropic etch in the mixing acid of hydrofluoric acid/hydrogen peroxide.
Described nanowhisker growth mother liquor is the one in the acetate of lead, zinc, cadmium, copper, antimony or iron, chlorate or nitrate.
Described crystal-silicon battery slice is the work in-process solar battery sheet of silicon single crystal, polysilicon, non-crystalline silicon or microcrystal silicon.
Metallic oxide nanocrystal palpus/Si matrix material prepared by aforesaid method is evenly, in order, particle diameter 10��50nm, thickness is at 20��100nm.
In the present invention, the nano whisker of growth not only can expand the absorption region of solar spectrum, it is to increase the utilising efficiency of sun power; Can also significantly improve the photoelectric transformation efficiency of silica-based solar cell sheet; But also there is the multiple action of antireflective, passivation crystal silicon material; Crystal silicon material surface passivation can be made; And greatly reduce sunlight reflection on silicon, it is possible to reduce cell piece surface Si3N4The consumption of antireflective film, reduces production cost greatly. The present invention also has following advantage:
1. sunlight is had stronger sorption by nano whisker/Si matrix material prepared by the present invention, battery surface luminous reflectance can be reduced, and its light trapping structure having can increase the probability of high energy exciton ionization by collision, produce multiple exciton effect, thus improve the photoelectric properties of silica-based solar cell.
2. the nano whisker of the present invention/Si matrix material shape looks are evenly and good stability, are able to take high temperature. After 900 DEG C of heating, the photoelectric properties of cell piece are still good.
3. the various performance parameters of treated silica-based solar cell sheet is all significantly improved. From Fig. 2 (embodiment 1): open circuit voltage/Voc promotes 37.5%, current density/Jsc promotes 193.2%, and packing factor/FF promotes 9.2%, and efficiency of conversion promotes 340.2%; From Fig. 3, Fig. 4 (embodiment 1): the absorption of solar battery sheet and reflecting properties all have and significantly promote.
4. the preparation technology of the present invention is simple, strong operability, cheaper starting materials and reusing, and production cost is low, high efficiency, is applicable to that industry is big produces.
Accompanying drawing explanation
Fig. 1 is embodiment 1 metallic oxide nanocrystal palpus/Si matrix material FESEM image (plane, section).
Fig. 2 is embodiment 1 metallic oxide nanocrystal palpus/Si matrix material photoelectric properties figure.
Fig. 3 is embodiment 1 metallic oxide nanocrystal palpus/Si matrix material absorptive character spectrogram.
Fig. 4 is embodiment 1 metallic oxide nanocrystal palpus/Si matrix material reflected light spectrogram.
Embodiment
Below by embodiment, the invention will be further described, and its object is only better to understand the content of the present invention but not limits the scope of the invention.
Embodiment 1
The preparation method of the metallic oxide nanocrystal palpus/Si matrix material catalytic growth that the present embodiment provides, concrete steps are as follows:
A) configuring the neutralized verdigris catalyst solution of 0.001mol/L, add the hydrofluoric acid that content is 40%, hydrogen fluoride concentration is 4.8mol/L; The mixed acid solution of hydrofluoric acid/hydrogen peroxide, wherein hydrogen fluoride concentration is 4.8mol/L, and hydrogen peroxide is 0.7mol/L; The zinc acetate nanowhisker growth mother liquor of 0.05mol/L.
B) crystal-silicon battery slice making p-n junction being flooded 15s in neutralized verdigris solution, transfer to rapidly in the mixed acid solution of hydrofluoric acid/hydrogen peroxide and etch 20s after taking-up, draining after taking out, blows dry.
C) the above-mentioned cell piece handled well is immersed in 30s in zinc acetate nanowhisker growth mother liquor.
D) cleaning 1min in deionized water, after taking out, electricity consumption blowing is done.
E) with loft drier, the cell piece handled well is dried 5min at 150 DEG C.
Embodiment 2
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of neutralized verdigris in step a) catalyst solution be 0.0001mol/L, hydrofluoric acid concentration is 3.5mol/L.
Embodiment 3
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of neutralized verdigris in step a) catalyst solution be 0.5mol/L, hydrofluoric acid concentration is 6mol/L.
Embodiment 4
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of Silver Nitrate in step a) catalyst solution be 0.001mol/L, hydrofluoric acid concentration is 4.8mol/L.
Embodiment 5
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of platinum chloride in step a) catalyst solution be 0.001mol/L, hydrofluoric acid concentration is 4.8mol/L.
Embodiment 6
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of Silver Nitrate in step a) catalyst solution be 0.001mol/L, hydrofluoric acid concentration is 4.8mol/L.
Embodiment 7
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step a) mixed acid solution hydrofluoric concentration and is that 3.5mol/L, hydrogen peroxide concentration are 0.05mol/L.
Embodiment 8
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step a) mixed acid solution hydrofluoric concentration and is that 6mol/L, hydrogen peroxide concentration are 2mol/L.
Embodiment 9
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of zinc acetate in step a) nanowhisker growth mother liquor is 0.005mol/L.
Embodiment 10
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of zinc acetate in step a) nanowhisker growth mother liquor is 1mol/L.
Embodiment 11
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of plumbic acetate in step a) nanowhisker growth mother liquor is 0.05mol/L.
Embodiment 12
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the concentration of Cadmium chloride in step a) nanowhisker growth mother liquor is 0.05mol/L.
Embodiment 13
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step b) catalyst solution to immerse 5s, corrode 10s in mixing acid.
Embodiment 14
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step b) catalyst solution to immerse 5s, corrode 20s in mixing acid.
Embodiment 15
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step b) catalyst solution to immerse 5s, corrode 30s in mixing acid.
Embodiment 16
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step b) catalyst solution to immerse 15s, corrode 30s in mixing acid.
Embodiment 17
The preparation method of the present embodiment is identical with embodiment 1, and difference is in step b) catalyst solution to immerse 30s, corrode 30s in mixing acid.
Embodiment 18
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the dipping time of the pretreated cell piece of step c) in nanowhisker growth mother liquor is 10s.
Embodiment 19
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the dipping time of the pretreated cell piece of step c) in nanowhisker growth mother liquor is 60s.
Embodiment 20
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the Heating temperature of step e) heat treatment process is 100 DEG C, and heat-up time is 10min.
Embodiment 21
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the Heating temperature of step e) heat treatment process is 240 DEG C, and heat-up time is 5min.
Embodiment 22
The preparation method of the present embodiment is identical with embodiment 1, and difference is that the Heating temperature of step e) heat treatment process is 240 DEG C, and heat-up time is 10min.
The above better embodiment being the present invention, but the present invention should not be confined to the content disclosed in this embodiment. The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all in protection scope of the present invention.
Claims (4)
1. a metallic oxide nanocrystal palpus/Si matrix material catalytic growth method, concrete steps are as follows:
A) configuration of solution: the catalyst solution of (1) 0.0001mol/L��1mol/L, add the hydrofluoric acid of 1mol/L��6mol/L, (2) hydrofluoric acid of 0.05mol/L��6mol/L/hydrogen peroxide etching solution, the nanowhisker growth mother liquor of (3) 0.0001mol/L��5mol/L metal ion; Described catalyst solution is the one in copper, silver, platinum or the gold muriate of metal, acetate or nitrate; Described nanowhisker growth mother liquor is the one in the acetate of lead, zinc, cadmium, copper, antimony or iron, chlorate or nitrate;
B) pre-treatment of cell piece: the crystal-silicon battery slice making p-n junction is impregnated into 1��200s fast in catalyst solution, makes cell piece surface form metal oxide crystal seed; Being immersed to 1��200s in etching solution after taking-up, carry out anisotropic etch, draining after taking out, blows dry;
C) growth of nano whisker: be moved rapidly in mother liquor by above-mentioned cell piece 1��100s, carries out the growth etching of nano whisker;
D) carrying out washing treatment: with washed with de-ionized water 1��5min, blow dry;
E) thermal treatment: by the cell piece after washing at 100 DEG C��400 DEG C thermal treatment 1��30min.
2. metallic oxide nanocrystal palpus/Si matrix material catalytic growth method according to claim 1, it is characterised in that: described cell piece pre-treatment need to carry out anisotropic etch in the mixing acid of hydrofluoric acid/hydrogen peroxide.
3. metallic oxide nanocrystal palpus/Si matrix material catalytic growth method according to claim 1, it is characterised in that: described crystal-silicon battery slice is the work in-process solar battery sheet of silicon single crystal, polysilicon, non-crystalline silicon or microcrystal silicon.
4. the metallic oxide nanocrystal palpus/Si matrix material that prepared by method according to claim 1-3 any one, it is characterized in that: prepared metallic oxide nanocrystal palpus/Si matrix material is evenly, in order, particle diameter 10��50nm, thickness is at 20��100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410155767.1A CN103943725B (en) | 2014-04-18 | 2014-04-18 | A kind of metallic oxide nanocrystal palpus/Si matrix material and catalytic growth method thereof |
Applications Claiming Priority (1)
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| CN101220515A (en) * | 2007-09-28 | 2008-07-16 | 天津大学 | Method for producing metallic oxide crystal whisker |
| CN101533889A (en) * | 2009-04-22 | 2009-09-16 | 北京理工大学 | Preparation method of ZnO nano crystal whisker reinforced silicon-based lead zirconate titanate piezoelectric composite thick film |
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| CN101220515A (en) * | 2007-09-28 | 2008-07-16 | 天津大学 | Method for producing metallic oxide crystal whisker |
| CN101533889A (en) * | 2009-04-22 | 2009-09-16 | 北京理工大学 | Preparation method of ZnO nano crystal whisker reinforced silicon-based lead zirconate titanate piezoelectric composite thick film |
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